Chapter 14. Sample Preparation For and Examination With The Scanning Electron Microscope - Petrographic Methods of Examining Hardened Concrete - A Petrographic Manual, July 2006 - FHWA-HRT-04-150

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Federal Highway Administration > Publications > Research Publications > 04150 > Petrographic Methods of Examining Hardened Concrete: A
Petrographic Manual
Publication Number: FHWA-HRT-04-150

Date: July 2006
Chapter 14. Sample Preparation for and Examination With

The Scanning Electron Microscope
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14.1 OVERVIEW
The application of the SEM in petrographic analysis of cementitious materials and concrete microstructure (Bentz
and Stutzman, 1993; Struble and Stutzman, 1989; Stutzman, 1990, 1991,1993; Stutzman and Bentz, 1993) is
becoming increasingly common. SEM imaging provides detailed images of the microstructure that augment those
from stereo and optical microscopy. The primary advantages are the high-contrast images of the microstructure, the
high spatial resolution of the images, and the ability to perform simultaneous imaging and chemical analysis. This
chapter presents an overview of the SEM and includes guidelines for specimen preparation, common imaging
methods, and image processing and analysis for quantitative microscopy.
14.2 SCANNING ELECTRON MICROSCOPE

The SEM (figure 173) scans a focused beam of electrons across the specimen and measures any of several
signals resulting from the electron beam interaction with the specimen. The most commonly used imaging modes
are secondary electron, backscattered electron, and x ray. Images are monochrome since they reflect the electron
or x&ray flux resulting from the beam⁄specimen interaction. Computer-based image processing and analysis make
routine quantitative imaging possible.
Figure 173. Scanning electron microscope.
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14.2.1 Secondary Electron Imaging
Secondary electrons (SE) are low-energy electrons produced as a result of an inelastic collision of a primary beam
electron with an electron of an atom within the specimen (Goldstein, et al., 1992). Because of their low energy, they
are readily absorbed and only those produced near the surface escape, producing the detailed images of surface
topography. The apparent shadowing in the image is a result of the absorption of the SEs by intermediary parts of
the specimen. The maximum depth of SE emission is reported to be about 1 nanometer (nm) in metals and 10 nm
in insulating materials, depending on the beam accelerating voltage (Goldstein, et al., 1992). Specimens intended
for secondary imaging benefit from a conductive coating of a heavy metal such as gold or gold/palladium to
increase secondary electron flux, improving the imaging signal. SE images are used to study particle size, shape,
surface roughness, and fracture surfaces.
SE images of fracture surfaces of hardened cement paste (figures 174 and 175) show a platy, or foil-like, calcium
silicate hydrate (CSH) (figure 174)-slender fibers of calcium silicate hydrate and, along the base of the image,
calcium hydroxide (CH) (platy habit). Figure 175 exhibits plates of CH (typical hexagonal habit) and the needle-like
habit of ettringite. The existence of the characteristic morphologies depends on the availability of void space for
uninhibited growth.
SE imaging is therefore particularly useful in the examination of early-age paste microstructure, high-magnification
imaging, examination of secondary crystal growth and fragments of material that may be plucked from a larger
specimen, and examination of aggregate texture. Knowledge of the morphological characteristics and bulk
chemistries of the hardened cement paste and mineral constituents aids in their identification. Although SE imaging
is useful for examining surface texture, the rough surface makes measurements of phase abundance unreliable. As
the hardened cement paste matures, filling of the void spaces eliminates the well-formed crystals shown in these
figures, with the resulting microstructure appearing to be nondescript. Backscattered electron and x-ray imaging are
ultimately more useful in the examination of these microstructures.
14.2.2 Backscattered Electron Imaging
Backscattered electrons (BE) are high-energy electrons (typically greater than 50 electronvolts (eV)) that have
undergone multiple elastic scattering events within the specimen. The greater energy results in a larger interaction
volume and lower spatial resolution compared to the SE image. However, the BE image contrast is generated by
the composition of the different phases relative to their average atomic number and is observed by the differential
brightness in the image.
Figure 174. SE image showing platy or foil-like CSH, fine bundles of CSH fibers and platy CH (top).
Figure 175. SE image showing platy CH and ettringite needles and also plate-like CH morphology (bottom).
The backscatter coefficient (η) is a measure of the BE fraction for a pure element (Z), which may be estimated using
the equation in figure 176 from Goldstein, et al. (1992):
Figure 176. Equation to estimate backscatter coefficient from Goldstein, et al. (1992).
The BE coefficient of a multi-element phase is estimated using the mass fractions (Ci) and ? values for each
constituent:
Figure 177. Equation to estimate BE coefficient of a multielement phase.
Contrast between constituents can be calculated as:

Figure 178. Equation to calculate contrast between constituents.
Table 26 lists some phases found in cements and hardened cement pastes, in descending order of their gray-level
intensity. Using the contrast equation (figure 178), initial estimates may be made to see if constituents can be
distinguished on the basis of their BE intensities. The contrast (6.8 percent) between alite ( = 15.06) and belite
( = 14.56) is relatively strong, whereas that between belite and cubic aluminate ( = 14.34) at 1.5 percent is
usually too weak to distinguish these constituents. Detector specifications usually quote a 0.5 resolution. In
difficult situations, a slower scan rate may improve the signal-to-noise ratio to allow distinction. In many of these
cases, however, the phases are chemically distinct and the use of x-ray microanalysis will allow their discrimination
and identification. Two factors do affect the gray-level intensity of a constituent: (1) porosity within a phase lowers its
Z value and will make it appear darker than expected and (2) a sol d solution, if present, will also influence the
intensity of a phase proportional to its deviation from these idealized compositions. Examples of these include
porosity within CSH for the former and zoning within the ferrite phase for the latter. In general though, anhydrous
cement appears brightest, followed by calcium hydroxide, calcium silicate hydrate, and aggregate. Voids appear
dark.
Figures 179 through 181 provide a comparison of stereomicroscopy and SEM BE and SE imaging. The
stereomicroscopic image (figure 179) has a field width of about 26 mm, showing a cross section of pavement
concrete exhibiting alkali-aggregate reaction. The SEM image (figure 180) illustrates the same microstructure, but
with image contrast based on BE. Figure 181 is another section of the same pavement, but with an SE image of the
surface topography. Features such as aggregate, air voids, and fractures are visible in each of the micrographs.
The SEM BE and stereomicroscopic images are the most similar as they are both of polished sections.
For both image types, feature identification is made by recognizing a feature as an aggregate, cement paste binder,
air void, or fracture. The sand in the SEM image appears as a uniform shade of gray with some brighter grains. The
coarse aggregate has a more varied BE signal reflecting the multiphase composition. Identification of the aggregate
mineralogy is made in subsequent figures.
Table 26. Cement and hydration product constituents, chemical composition, and backscattered electron
coefficient (η).
Phase Composition η
Cement Phases
Ferrite Ca2(Al,Fe)2O5 16.65 0.1860
Free lime CaO 16.58 0.1882
Alite Ca3SiO5 15.06 0.1716
Belite Ca2SiO4 14.56 0.1662
Arcanite K2SO4 14.41 0.1652
Aluminate-cub. Ca3Al2O6 14.34 0.1652
Aluminate-ort. NaCaAl3O9 13.87 0.1588
Aphthitolite (Na,K)2SO4 13.69 0.1577
Syngenite K2Ca(SO4)2H2O 13.60 0.1556
Anhydrite CaSO4 13.41 0.1535
Bassanite 2CaSO4·H2O 13.03 0.1489
Phase Composition η
Cement Phases
Gypsum Ca(SO4)·2H2O 12.12 0.1381
Thenardite Ca(SO4)·2H2O 10.77 0.1249
Periclase MgO 10.41 0.1213
Hydration and secondary products:
Portlandite Ca(OH)2 14.30 0.1617
Tobermorite Ca5Si6O18H2 13.16 0.1539
Hemicarbonate [Ca2Al(OH)6][0.5 H2O 0.25 CO3 aq] 12.39 0.1406
Hydrogarnet Ca3Al2(OH)12 12.30 0.1398
Gypsum Ca(SO4)·2H2O 12.12 0.1381
Plombierite Ca5Si6O16(OH)2 8H2O 12.09 0.1380
Monosulfate [Ca2Al(OH)6][0.5(SO4)3H2O] 11.66 0.1324
Ettringite {Ca6[Al(OH)6]2·24H2O}[(SO4)3·1.5H2O] 10.79 0.1222
Thaumasite Ca3Si(OH)6·24H2O (CO3)(SO4) 9.74 0.1097
Brucite Mg(OH)2 9.43 0.1085
Hydrotalcite [Mg0.75Al0.25(OH)2](CO3)0.125(H2O)0.5 9.09 0.1042
Aggregate phases:
Calcite CaCO3 12.56 0.1422
Dolomite CaMg(CO3)2 10.87 0.1237
Quartz SiO2 10.80 0.1254
The fracture surface (figure 181) at about the same magnification shows the hardened cement paste, aggregates,
and some air voids; however, the rough surface makes identification of these constituents more difficult. This mode
of SEM imaging is best suited for higher magnification examinations of microstructural features.
The images presented in figures 179 through 184 show that the SEM can work like a stereomicroscope in low-
magnification screening of concrete microstructures. It may also be used to examine paste microstructures as seen
in figures 185 and 186 with lower and higher magnification images.
Figure 179. Stereomicroscopic image.
Figure 180. Backscattered electron image (same specimen).
Field width is about 15 mm.
Figure 181. Secondary electron image of a fresh-fracture surface from concrete.
Field width is about 15 mm.

Figure 182. Top. Paired image at successively greater magnification of stereomicroscope (white light)
images and SEM BE images: Field width is 11 mm.
Figure 183. Middle. Field width is 3 mm.
Figure 184. Bottom. Field width is 1.5 mm.
Figure 185. Backscattered electron image of an epoxy-impregnated, polished cross section of concrete
(field width is 2 mm).
a = aggregate, c = residual cement, ch = calcium hydroxide, ip = calcium-silicate-hydrate, inner product, and op =

calcium-silicate-hydrate, outer product
Figure 186. Backscattered electron image of an epoxy-impregnated, polished cross section of concrete
(field width is 1 mm).
a = aggregate, c = residual cement, ch = calcium hydroxide, ip = calcium-silicate-hydrate, inner product, and op =

calcium-silicate-hydrate, outer product
14.2.3 X-Ray Microanalysis
X-radiation is produced when a specimen is bombarded by high-energy electrons. The beam electrons eject inner-
shell electrons that are then replaced by outer-shell electrons. This replacement results in emission of an x ray
characteristic for that element. The x-ray energy level is displayed as the number of counts at each energy interval
and appears as peaks on a continuous background (figure 187), referred to as an energy-dispersive x-ray spectrum
(EDX).
Figure 187. EDX spectrum.
Peak positions are specific to a particular element, intensity (height) is proportional to its relative abundance. This
spectrum, from ettringite, exhibits that mineral’s characteristic composition with oxygen, aluminum, sulfur, and
calcium. Note that units on the horizontal axis are kiloelectronvolts (keV).
The peaks are designated as k, l, or m. The positions of the peaks are characteristic of a specific element, so phase
identifications are made by examination of peak positions and relative intensities (figure 188).
The x-ray signal is used for: (1) spectrum analysis for qualitative and quantitative chemical analyses (figure 188),
(2) line scan analysis to plot relative concentration of selected elements along a line (figure 189), (3) x-ray imaging
(XR) of element spatial distribution and relative concentrations (figure 190), and (4) an aid in phase identification
through its chemical signature. Phase identification is not absolute as in x-ray powder diffraction; however,
combining criteria (e.g., BE signal brightness, morphology, associations with other constituents, and chemical
composition) provides a rather strong basis for identification. Coupling microscopy with x-ray powder diffraction data
is also useful as it can be used to limit the elements in the potential compounds to those present in the specimen.
Mass concentration to a few tenths of a percent can be detected using an energy dispersive x-ray detector. The
relative accuracy of quantitative analysis (using certified standards) is about ±20 perce t for concentrations of about
1 percent, and ±2 percent for concentrations greater than 50 percent. More details on x-ray microanalysis may be
found in Goldstein, et al. (1992).
Figure 188. EDX spectra for ettringite (top left), monosulfate (top right), calcium hydroxide (bottom left), and
calcium-silicate-hydrate (bottom right) aid in phase identification characteristics.
The peaks and their relative intensities are affected by the accelerating voltage of the microscope beam (figure
191). If the voltage is too low, then the beam energy may not be capable of generating the characteristic radiation.
For example, the iron K line occurs at 6.4 keV and requires about 11 keV for adequate excitation. Accelerating
voltages between 12 and 15 keV provide for reasonable BE and x-ray imaging. Lower accelerating voltages
decrease the interaction volume, increasing resolution, but with a loss in efficiency in generating higher energy x
rays.
Lower beam energies are not as efficient in exciting high-energy x rays, and the lower x-ray absorption accentuates
the low-energy x rays. High beam energies result in greater absorption in the lower energy range. For cements, an
accelerating voltage of 12 to 15 keV balances the need for adequate beam energy without excessive absorption of
lower energy x rays. Higher beam energies are favored for SE imaging as they result in increased depth of field and
smaller beam diameters and, thus, greater resolution.
Figure 189. Fence diagram created by collecting a series of EDX spectra along an emplacement of ASR gel
(the gel composition rapidly becomes much like the bulk CSH once outside the aggregate and the source of
reaction).
Figure 190. Plots of element spatial distribution are generated through x-ray imaging.
Figure 191. Effects of different accelerating voltage on x-ray spectra of ettringite show the loss of low-
energy peaks at high accelerating voltages and the opposite effect at low voltages.
X-ray spectra (low to high energy, keV, left to right) for different accelerating voltages. Note that, in this case,
accelerating voltages are given as "kv," which are the same as keV, as discussed earlier.
14.3 SPECIMEN PREPARATION
14.3.1 Overview
The SEM may be used to examine portland cement clinker, cement powder, cement pastes, mortars, and hardened
portland cement concrete. Specimen preparation uses an epoxyimpregnated, polished section where the epoxy
resin permeates the material’s pore system or encases powder particles. The specimens are then cut or ground to
expose a fresh surface, and that surface is then polished using a series of successively finer grades of diamond
paste. This polishing stage is necessary to remove cutting and grinding damage, exposing an unaltered cross
section of the material’s microstructure. Polished thin sections prepared as described in section 5.3.4 can be
examined both with transmitted light and with the SEM (see figures 121 through 123). Sahu, et al. (2001) described
coupled transmitted-light and SEM examinations of thin sections.
Epoxy impregnation of the pore system serves two purposes: (1) it fills the voids and, upon curing, supports the
microstructure, serving to restrain it against shrinkage cracking, and (2) it enhances contrast among the pores,
hydration products, and cementitious material. With relatively high-permeability materials or powders such as
clinker or portland cement, an epoxy of low viscosity is necessary, whereas for the less-permeable cement pastes
and concretes, an ultra-low viscosity epoxy aids in rapid infiltration of the pore structure. Examples of epoxies that
are used for impregnation/embedment are LR White (hard grade) (ultra-low viscosity) and EPOTEK 301 (medium
low viscosity) (chapter 2); other suitable materials may be used.
BE and x-ray imaging requires a highly polished surface for optimum imaging and x-ray microanalysis (Stutzman
and Clifton, 1999). Rough-textured surfaces diminish the image quality by reducing contrast and loss of feature
definition. In addition, the lack of a polished specimen makes quantitative estimates arduous, as the surface is no
longer planar. Sawcut surfaces that have not been epoxy-impregnated, or polished, do not present the true
microstructure and are difficult to examine and interpret without bias. The sawing operation damages the
microstructure through the creation of a series of fractures, which are then enhanced with subsequent drying
shrinkage. For SE imaging, the saw damage dominates the topographic features, and particulate matter deposited
on the surface may be mistaken for undisturbed material. Polished, epoxyimpregnated specimens are relatively
simple to prepare and the above-mentioned difficulties can be avoided.
A comparison of BE images of a sawcut surface (figure 192) with an epoxy-impregnated, polished surface (figure
193) of the same concrete core illustrates the marked differences in feature clarity and artifacts. In figure 192, the
sawcut surface exhibits cracking that resulted from drying shrinkage of a surface-damaged specimen. The surface,
being rough and partly covered with particulate matter, exhibits little phase-related contrast. The image shows an
aggregate at the base; however, aside from the uniform hardened paste, no distinct hydration products can be
discerned. The epoxy-impregnated, polished specimen (figure 193) shows microstructural feature clarity not seen in
the images in figure 192. Here, the aggregate is not only clearly seen, but one can also distinguish between
siliceous and carbonate aggregate by gray level. The residual cement grains appear bright, and large voids within
both the paste and the aggregate are dark. In the higher magnification image (bottom), the hardened cement paste/
aggregate interfacial zone is shown. The residual cement grains are the brightest feature, followed by CH,
carbonate aggregate, CSH, and finally the black pores. A highly polished surface also aids in x-ray imaging. Figure
194 illustrates the use of x-ray imaging of a region shown in the BE image (top) to examine element spatial
distribution (bottom). In this example, visual assessment of calcium, aluminum, and sulfur images allow one to
locate monosulfate within the hardened cement paste. Referring back to the BE image shows the monosulfate as a
uniform gray that is slightly darker than CSH, with a platy parting.
Figure 192. BE images of unimpregnated, sawed surface (the sawed surface is rough with residual
particulate matter, yielding poor contrast and shadowing that make interpretation of BE and EDX images
difficult).
Figure 193. BE images of the impregnated, polished surface from the same concrete (polished surface
presents optimum BE and EDX imaging characteristics).
Figure 194. Polished section of hardened portland cement paste imaged using the BE signal clearly shows
the constituent phases (residual cement (RC) appears brightest, followed by CH, CSH, and other hydration
products) (top); EDX image (bottom) shows regions of intermediate-intensity calcium (blue), intermediate-
intensity aluminum (purple), and highintensity sulfur (yellow), defining locations of monosulfate that could
not be distinguished on a rough surface (field width is 73 µm).
14.3.2 Materials for Sample Preparation
A list of equipment and materials necessary for the preparation of polished specimens is given in table 27. For
some items, substitution may be possible if comparable supplies are available in the laboratory. The list is
presented in order of use of the equipment or supplies.
Table 27. Equipment and supplies for preparation of polished sections.
Item Purpose
Diamond blade slab saw Large-sized sample slabbing
Diamond blade wafering saw Cutting of thin (millimeter-sized) sections
Propylene glycol Diamond-saw cutting lubricant
Alcohol: 200-proof ethanol Cutting lubricant, cleaning aid
Item Purpose
Ultrasonic bath Specimen cleaning
Specimen jars and lids For replacement steps
Potting epoxies (medium and low viscosity) For powders and hardened pastes
Dye, blue or red, alcohol-miscible LTo estimate alcohol replacement depth
Refrigerator Epoxy storage
Vacuum chamber and pump Vacuum impregnation
Drying/curing oven Capable of at least 65 °C
Glass plate (400 by 400 mm) Smooth surface for grinding
Lapidary wheel (minimum 200 mm) Grinding and polishing
Mold cups Potting specimens
Aluminum foil (extra heavy duty) For forming odd-sized specimen molds
Mold release Facilitates removal of specimen/epoxy
Metal trays to hold specimens Contains any leaking epoxy
Diamond pen Label engraving
Abrasive papers (silicon carbide) Coarse to fine grinding, 100 to 600 grit
Polishing cloths (low-relief) 6µm and finer polishing
Diamond paste for polishing 6, 3, 1, 0.25 µm in non-aqueous suspension
Lint-free cloths Specimen handling and cleaning
Compressed air Specimen cleaning and drying
Vacuum desiccators Specimen storage
14.3.3 Polished Sections of Cement and Pozzolan Powders
Powder mounts are prepared by suspending cement powder in epoxy, curing the epoxy, and cutting and polishing a
surface of the powder/epoxy composite. The cement powder is mixed in about 5 grams (g) of epoxy, using enough
cement to form a stiff ball. The cement/epoxy mixture is placed in a mold container and pressed to fill the base of
the mold. The mixture is then consolidated in the sample mold by sharply tapping it on the laboratory bench top,
and the epoxy is cured in accordance with the manufacturer&s guidelines. After curing, the specimen is removed
from the mold and labeled and a fresh surface is exposed using a wafering saw or by grinding. Examples of this
application may be found in Struble and Stutzman (1989) and Stutzman (1990).
14.3.4 Preparation of Cement Paste, Mortar, and Concrete Sections
Cement pastes, mortars, and concretes may be prepared in two ways: (1) dry potting and (2) wet potting. Dry
potting is used when the specimen has been dried before, when drying shrinkagerelated cracking is not of concern,
or when rapid preparation is needed. Wet potting is used to prepare a polished section where the material has not
been dried and therefore has not undergone any drying shrinkage. Cracks observed in wet-potted specimens may
then be ascribed to physical or chemical processes acting upon the concrete prior to specimen preparation, and not
to dryingrelated shrinkage resulting from preparation techniques.
Dry-specimen potting involves taking a sawed section or block of material and drying the specimen at a low
temperature (less than 65 °C). Removal of water is necessary as it can interfere with polymerization of the epoxy.
The specimen is then placed in a container and surrounded by epoxy, leaving the top surface exposed to laboratory
air, allowing the lowviscosity epoxy to be drawn into the microstructure by capillary suction. To speed infiltration, or
when using a medium-viscosity epoxy, the specimen may be immersed in epoxy and a vacuum drawn to remove
the remaining air. Vacuum-impregnation procedures are described in chapter 5 (section 5.3.4.2). Upon release of
the vacuum, the epoxy is forced into the pore system. The epoxy is cured at a low temperature (65 °C) and is then
ready for cutting and polishing.
Wet-specimen potting is a three-step process: (1) the pore solution is replaced with alcohol (200-proof ethanol), (2)
the ethanol is replaced with a low-viscosity epoxy, and (3) the epoxy is then cured. The slab and wafering saws are
lubricated with propylene glycol or isopropyl alcohol to keep the specimen from drying when cutting. The cut section
is then placed in a lidded jar filled with 200-proof ethanol for the alcohol-pore solution replacement stage. The use
of a companion specimen allows one to gauge the time necessary for the alcohol-pore solution replacement. This
companion specimen is usually a remnant from the specimen after trimming. This specimen is placed in a jar filled
with ethanol dyed a deep red or blue using any alcoholmiscible dye. By splitting or sawing the companion specimen
after a period of time, the depth of replacement can be observed by the depth of dye coloration. When this front is
equal to half the section thickness, the pore solution in the section has been replaced by alchol. The section is then
placed in a container with the low-viscosity epoxy. The time necessary for epoxy replacement of the alcohol is at
least equal to that required for the first replacement stage. In the NIST laboratory, we allow about 1.5 times the pore
solution-alcohol replacement time for that of the epoxy-alcohol replacement. Implicit in this method is that the
thinner the section, the shorter the time that is required for each stage. The specimen is placed in a mold with fresh
epoxy, which is then cured at low temperatures according to the manufacturer’s directions. The specimen is then
ready for the cutting and polishing stages.
14.3.5 Cutting and Grinding
The cutting, grinding, and polishing steps are common to all preparations in order to expose a fresh surface.
Diamond-blade slab or wafering saws, lubricated using propylene glycol, are suitable for exposing a fresh surface.
This surface needs to be smoothed by grinding. Abrasive papers of 220, 320, 400, and 600 grit (silicon carbide
paper) used dry are also suitable for rapid removal of material by grinding. VTRC uses diamond-impregnated
lapping films (chapter 2) (available in 125, 75, 45, 30, 15, 9, and 6 µm) at this stage. Using successively finer
grades of abrasive paper removes damage produced by the earlier step. After grinding with the 600 grit paper, the
surface is smooth enough for polishing with the diamond pastes. Visual examination of the specimen allows one to
identify when the abrasive has cut the entire surface. Grinding striations on the specimen surface indicate that the
grit has removed a layer of material. By alternating grinding directions by 90 degrees, one can ensure that the entire
surface has been ground. These operations damage the specimen surface, necessitating a polishing step that is
described next.
14.3.6 Polishing
Polishing removes the damage imparted by the sawing and grinding operations (figures 192 and 193). This stage
involves use of a sequence of successively finer particle-size diamond polishing pastes ranging from 6 to 0.25 µm,
and a lap wheel covered with a low-relief polishing cloth. This may be performed manually or, for greater sample
throughput, a semi-automated polisher may be used.
14.3.7 Coating for Examination
Variable-pressure electron microscopes are operable with excellent results when using uncoated specimens. For
those systems that require a high vacuum, a thin coating of carbon serves to dissipate excess charge from the
specimen while exhibiting little effect on image contrast and little interference with elements of interest. Metal
coatings such as gold or gold palladium are suitable for secondary imaging of topographic features. However, their
x-ray lines interfere with elements of interest in cementitious materials (sulfur) and the heavy metal decreases BE
contrast.
14.4 IMAGING STRATEGIES FOR SEM

The various SEM examination modes are discussed in section 14.2. That information, together with the specific
issues regarding the study at hand, guided mode selection. For general concrete characterization and investigation
of materials-related distress, the coupling of information gained through BE and EDX examination modes has been
found most useful. Review information in chapters 3, 8, and 10 through 13 and Van Dam (2002b) regarding the
planning of examinations. Typical settings for routine examinations in the three basic modes are outlined in table
28.
Examples of the use of BE and EDX techniques are given in sections 14.2.2 and 14.2.3. Examples of their use in
investigating AAR are shown in chapter 10. The high resolution and the ability to perform chemical analyses make
these modes ideal for examining HCC paste. The hydration products appear as an intermediate gray, and the
residual cement appears to be bright. The aggregate may be recognized using both its gray level and uniformity
and its shapes. Silicates such as quartz appear to be slightly darker than the cement paste (figures 185 and 186),
whereas feldspars can be distinguished by the presence of Ca, or Na and K. Calcium carbonate aggregate appears
similar in gray level to that of the paste; dolomite can be distinguished from calcite by its slightly darker gray level
and the presence of Mg (figure 196). In differentiating carbonate aggregates from hydration products, the feature&s
uniformity and shape are characteristics that are useful in distinguishing aggregates from the hardened paste atrix
(figures 197 and 198).
Close examination of the microstructure of a 28-day hardened portland cement paste is demonstrated in figure 194
in which BE and EDX images display constituents of the paste.
Table 28. Typical SEM settings for routine examinations.method.
Secondary electron imaging (SEI)

Moderate accelerating voltage (higher values gain image depth)
Low probe current (smaller probe size provides greater resolution)
Relatively heavy metal coating (to provide continuous film and
increase SE yield)
Backscattered electron imaging

(BEI) Low accelerating voltage
High probe current (resolution limited by accelerating voltage)
Carbon coating or no coating
dwell times because of lower BE flux
X-ray imaging/x-ray
microanalysis(EDX) 12 to 10 keV, to about 8 keV if no Fe
High probe current; coating rules same as for BEI
Longer dwell times because of much lower x-ray flux
For cement pastes, residual cement grains appear brightest, followed by the hydration products CH, CSH, and the
darkest, being the epoxy-filled pore spaces (review table 26). Other constituents such as ettringite and monosulfate
appear similar in gray level to that of CSH and require x-ray analysis for location and identification. Both of these
phases do show greater uniformity and perhaps a slightly darker gray than that of CSH, and they also exhibit a platy
parting that is, in part, a result of desiccation. X-ray imaging (figure 194, lower images) demonstrates how
examination for regions of intermediate-intensity calcium (blue), intermediate-intensity aluminum (purple), and high-
intensity sulfur (yellow) define locations of monosulfoaluminate.
For the cement grain (figure 194), the ferrite phase appears brightest in the BE (upper) image, followed by alite,
belite, aluminate, and periclase. X-ray imaging facilitates identification of periclase, alkali sulfates, and calcium
sulfates. Figures 198 and 199 show that for a 28-day hardened cement paste microstructure, polishing yields clear
definition of the constituents?the black pore space filled with the cured epoxy, the bright grains of residual cement
(C), the intermediate-gray CSH, and the somewhat brighter gray CH.
14.5 QUANTITATIVE METHODS IN MICROSCOPY
14.5.1 Point-Count Analysis
The relationship between area fraction and volume fraction has been recognized for a long time and was
mathematically derived by Chayes (1956).
There are three established methods for determining the area percentage of a phase in a planar section (also
review section 6.3.2): (1) the Delesse method of tracing and weighing each phase group, (2) the Rosiwal-Shand
linear traverse method, and (3) the Glagolev-Chayes point-count method.
The Glagolev-Chayes method, or point-count method, is perhaps the most widely used technique in quantitative
mineralogical analysis using a microscope. As the name implies, this technique involves sampling the
microstructure using a grid of points and identifying the phase falling underneath each point. The rule for selecting a
grid, magnification, and crystal size is to select a point spacing slightly greater than the crystal size (i.e., adjacent
points should not fall on the same crystal). Additional points are measured by moving the specimen to a new field of
view and again counting the phases under the points. The point-count method is relatively simple, yet provides a
reliable means to measure phase abundance physically, using a direct measure of the microstructure.
Three principal sources of error were identified by Hofmänner (1975) for consideration when point counting:
Random sample errors.

Errors in identification by the observer.
Measurement errors.
For these exercises, it is assumed that a representative sample was collected and that the sample size was
reduced using proper practices. The measurement error of the analysis is related to the total number of points
counted, with the absolute error at the 96-percent confidence interval given using the equation in figure 195:
Figure 195. Equation for percent error in the point-count method (at the 96-percent confidence level) based
on the the proportion of points on the phase of interest and the total number of all points counted.
where:
η = absolute error in percent
P = percentage of points of a phase
N = total of all points
The total error becomes smaller as the number of points counted increases; therefore, the greater the number of
points counted, the more reliable the measurement. An analysis of 4000 points should provide acceptable precision
for phase abundance analysis.
Mass percentages may be calculated by multiplying the volume fractions by the specific gravity of the
corresponding clinker phase and normalizing the totals to 100 percent.
In addition to phase abundance, measurement of crystal size, shape, and other parameters may be recorded.
Figure 196. BE image (right) of carbonate aggregate composed of darker gray dolomite (1) rhombs in fine-
grained matrix containing lighter gray calcite (6) (the gray-level intensity of calcite and dolomite is distinct,
and they can also be distinguished on the basis of the EDX spectra (left); field width is approximately 100
µm).
Figure 197. BE images of carbonate aggregate in concrete at 15X (field width of 8 mm).
Aggregate particle is to upper left in left image and lower right in right image. Uniformity and shape are useful in
distinguishing carbonate aggregate from a mortar matrix that contains phases of similar gray-level intensity.
Figure 198. BE images of carbonate aggregate in concrete at 400X (field width of 300 µm).
Aggregate particle is to upper left in left image and lower right in right image. Uniformity and shape are useful in
distinguishing carbonate aggregate from a mortar matrix that contains phases of similar gray- level intensity.
14.5.2 Image Processing and Analysis
Computer-based image processing and analysis may also be used to extract information from images, or
combinations of images. The BE and x-ray images of polished sections are best suited for this approach as they
use the planar section necessary for measurements. Features may be identified on the basis of their gray level
(figures 199 and 200) or through combinations of features from images, making use of both x-ray and BE
information (figure 201). Identification and measurement of residual cement particles in hydrated cement can be
accomplished by taking advantage of the cement particles& bright appearance in the BE image. They may be
isolated on the BE brightness alone. Similarly, coarse porosity appears black in the BE image and may also be
isolated and measured on this basis.
Figure 202 illustrates the use of BE and EDX images to calculate the percentage of CH in the paste. Information
from the analyses similar to those shown in figures 199 through 202 provide data on unhydrated cement, CH, and
paste porosity. As noted in chapter 9, these parameters can be used to form a comparative estimate of w/cm.
Badger, et al. (2001) reports on quantifying porosity by means of contrast in BE images to estimate w/cm.
A more difficult feature would be mapping the distribution of monosulfate in a hydrated cement paste. The BE
coefficient is not such that it is easily distinguishable from CSH. It does exhibit a greater uniformity and,
occasionally, platy parting. However, it is compositionally distinct, composed of calcium, aluminum, and sulfur, and
may be both identified and mapped using both the BE and x-ray images (figure 194) and quantified as described
here.
Figure 199. Gray-level histogram of hardened cement paste.
Figure 200. BE image of hardened cement paste (field width is 73 µm).
Figure 201. Pseudocolored image based on BE gray scale of figures 199 and 200 (red = residual cement,
blue = CH, black = CSH, and green = coarse porosity).Counting the number of pixels for each color allows
an estimate of the phase area fractions for this field of view.
Figure 202. Processing of BE and calcium x-ray images here highlights the CH location (analysis of the
binary image of CH distribution calculated 12 percent of the image field to be occupied by CH).
14.6 SUMMARY
Proper specimen preparation is necessary when using the SEM for the study of cementitious materials and
hardened HCC. Rough surfaces, such as those prepared using only fracture, sawcut, or rough-lapped preparations,
are not suitable. These preparations may actually create preparation-induced artifacts that are not representative of
the microstructure; create a surface that is difficult to describe; and not being planar, are unsuitable for estimates of
phase abundance. The BE and x-ray imaging modes are particularly sensitive to rough surfaces, which affect the
definition of the constituents through loss of contrast and signal shadowing.
Comparison of SEM and optical microscopic examinations of HCC show that the important features are
recognizable in both technologies. The much higher resolving power of the SEM, together with the elemental
analysis capabilities of the EDX microprobe, creates a tool that greatly expands our capabilities to study the
microstructure of HCC, including the interaction between the various cementitious materials being used today and
the microstructural effects of deterioration mechanisms.
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Page Owner: Office of Research, Development, and Technology, Office of Infrastructure, RDT
Topics: research, infrastructure, pavements and materials

Keywords: research, infrastructure, pavements and materials, petrography, hydraulic cements, portland cement,
concrete, aggregate, cracking, voids, microscope, alkali silica reaction (ASR), alkali carbonate reaction (ACR)
TRT Terms: research, facilities, transportation, highway facilities, roads, parts of roads, pavements , pavements,
concrete--testing--handbooks, manuals, etc, concrete--testing--handbooks, manuals, etc, petrographic
microscope, petrography, specimens
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Chapter 14. Sample Preparation For and Examination With The Scanning Electron Microscope - Petrographic Methods of Examining Hardened Concrete - A Petrographic Manual, July 2006 - FHWA-HRT-04-150

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1/22/2020 Chapter 14.

U.S. Department of Transportation

Federal Highway Administration Research and Technology

Publication Number: FHWA-HRT-04-150

Chapter 14. Sample Preparation for and Examination With

14.2 SCANNING ELECTRON MICROSCOPE

Figure 173. Scanning electron microscope.

14.2.1 Secondary Electron Imaging

14.2.2 Backscattered Electron Imaging

Figure 177. Equation to estimate BE coefficient of a multielement phase.

Contrast between constituents can be calculated as:

Figure 178. Equation to calculate contrast between constituents.

Ferrite Ca2(Al,Fe)2O5 16.65 0.1860

Free lime CaO 16.58 0.1882

Alite Ca3SiO5 15.06 0.1716

Belite Ca2SiO4 14.56 0.1662

Arcanite K2SO4 14.41 0.1652

Aluminate-cub. Ca3Al2O6 14.34 0.1652

Aluminate-ort. NaCaAl3O9 13.87 0.1588

Aphthitolite (Na,K)2SO4 13.69 0.1577

Syngenite K2Ca(SO4)2H2O 13.60 0.1556

Anhydrite CaSO4 13.41 0.1535

Bassanite 2CaSO4·H2O 13.03 0.1489

Gypsum Ca(SO4)·2H2O 12.12 0.1381

Thenardite Ca(SO4)·2H2O 10.77 0.1249

Periclase MgO 10.41 0.1213

Hydration and secondary products:

Portlandite Ca(OH)2 14.30 0.1617

Tobermorite Ca5Si6O18H2 13.16 0.1539

Hemicarbonate [Ca2Al(OH)6][0.5 H2O 0.25 CO3 aq] 12.39 0.1406

Hydrogarnet Ca3Al2(OH)12 12.30 0.1398

Gypsum Ca(SO4)·2H2O 12.12 0.1381

Plombierite Ca5Si6O16(OH)2 8H2O 12.09 0.1380

Monosulfate [Ca2Al(OH)6][0.5(SO4)3H2O] 11.66 0.1324

Ettringite {Ca6[Al(OH)6]2·24H2O}[(SO4)3·1.5H2O] 10.79 0.1222

Thaumasite Ca3Si(OH)6·24H2O (CO3)(SO4) 9.74 0.1097

Brucite Mg(OH)2 9.43 0.1085

Hydrotalcite [Mg0.75Al0.25(OH)2](CO3)0.125(H2O)0.5 9.09 0.1042

Calcite CaCO3 12.56 0.1422

Dolomite CaMg(CO3)2 10.87 0.1237

Quartz SiO2 10.80 0.1254

Figure 179. Stereomicroscopic image.

Figure 180. Backscattered electron image (same specimen).

Field width is about 15 mm.

Figure 181. Secondary electron image of a fresh-fracture surface from concrete.

Field width is about 15 mm.

Figure 183. Middle. Field width is 3 mm.

Figure 184. Bottom. Field width is 1.5 mm.

a = aggregate, c = residual cement, ch = calcium hydroxide, ip = calcium-silicate-hydrate, inner product, and op =

a = aggregate, c = residual cement, ch = calcium hydroxide, ip = calcium-silicate-hydrate, inner product, and op =

14.2.3 X-Ray Microanalysis

Figure 187. EDX spectrum.

14.3 SPECIMEN PREPARATION

14.3.2 Materials for Sample Preparation

Table 27. Equipment and supplies for preparation of polished sections.

Diamond blade slab saw Large-sized sample slabbing

Diamond blade wafering saw Cutting of thin (millimeter-sized) sections

Propylene glycol Diamond-saw cutting lubricant

Alcohol: 200-proof ethanol Cutting lubricant, cleaning aid

Ultrasonic bath Specimen cleaning

Specimen jars and lids For replacement steps

Dye, blue or red, alcohol-miscible LTo estimate alcohol replacement depth

Refrigerator Epoxy storage